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2024 | OriginalPaper | Buchkapitel

14. Covalent, Metallic, and Secondary Bonding

verfasst von : Rick Ubic

Erschienen in: Crystallography and Crystal Chemistry

Verlag: Springer International Publishing

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Abstract

This chapter introduces the concepts of bonding, coordination, and packing fraction. We start with covalent bonding, encompassing both valence bond theory and molecular orbital theory, then move to metallic bonding, the Hume-Rothery Rules, and band theory; and we finish with Van der Waals forces and hydrogen bonding. A biographical sketch of Johannes Diderik van der Waals is also included.

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Vorheriges Kapitel Quantum Theory

Nächstes Kapitel Ionic Bonding

Nur mit Berechtigung zugänglich

The valence level is the outermost electron shell of an atom, containing valence electrons which are accessible for the formation of chemical bonds.

Electrons are delocalized if they are associated with more than one bond. Valence bond theory does not allow for bond delocalization, which is one of its weaknesses.

Paramagnetic materials are weakly attracted by external magnetic fields whereas diamagnetic materials are repelled by magnetic fields.

As for single atoms, the first superscript in the molecular notation is the multiplicity (the number of unpaired electrons plus one). Instead of the symbols S, P, D, or F to indicate a total orbital angular momentum quantum number equal to 0, 1, 2, or 3, we use the Greek equivalents, Σ, Π, Δ, or Φ. The subscript “g” indicates the state’s parity. If inverting the electron’s position with respect to the molecular mass centre leaves the wavefunction unchanged, it is labeled “g” for gerade (even); otherwise, it is “u” for ungerade (odd). Finally, for the Σ states, a superscript is used to indicate whether the state is symmetric, “+”, or antisymmetric, “−”, upon reflection through any plane containing the internuclear axis.

The ultimate tensile strength, or simply tensile strength, is the maximum stress that a material can withstand before breaking while being stretched or pulled.

Remember, metallic bonding isn’t fully broken until the metal boils.

More strictly, we mean here only recoverable, or elastic, deformation, as this kind of deformation involves only the stretching/compression of atomic spacings.

Hume-Rothery earned a first-class honours degree in chemistry at Oxford and a PhD from the Royal School of Mines (now part of Imperial College London) despite being totally deaf from the age of 18. He went on to found the Department of Metallurgy (which is now the Department of Materials) at the University of Oxford in the mid-1950s. One of his students there was William “Bill” Pearson.

In 1819, Pierre Louis Dulong and Alexis Thérèse Petit found that the heat capacity of a mole of many solid elements is about 3R or ~ 25 J/K (the gas constant, R, had not yet been defined).

A direct semiconductor is one for which the peak in the valence-band energy aligns with the minimum in the conduction-band energy. An indirect semiconductor is one for which the peak in the valence-band energy does not align with the minimum in the conduction-band energy.

Not to be confused with metalloids, which, although there is no standard definition, are typically described as elements with properties between (or a mixture of) those of metals and nonmetals. The six most commonly recognised metalloids include B, Si, Ge, As, Sb, and Te. Other elements sometimes included are C, Al, Se, Po, and At. Although there is some overlap in the sets of semimetals and metalloids, the terms are not synonymous. Unlike metalloids, semimetals can also be compounds, like HgTe; and unlike metals, semimetals have both electron and hole charge carriers but typically in smaller numbers than in a metal. The electrical properties of semimetals are between those of metals and semiconductors.

Strongly correlated materials are defined by the fact that the behaviour of their electrons cannot be described effectively without considering interaction. Theoretical models of the electronic structure of these strongly correlated materials must include electronic correlation (interaction) to be accurate. Such materials can show unusual electronic or magnetic properties, including multiferroic behaviour, metal-insulator transitions, high-T_c superconductivity, heavy-fermion behaviour, half-metallicity, and spin-charge separation. Many transition-metal oxides fall into this category.

Charles formulated the original law in unpublished work during the 1780s. Joseph Louis Gay-Lussac mentions it in his “Recherches sur la dilatation des gaz et des vapeurs” of 1802.

Clapeyron never explains why he choose the letter R for his constant, and some have seen it as an homage to Henri Victor Regnault, who provided much of the empirical data for its derivation (although it probably just meant rapport “ratio.”)

A mole of gas contains N_A molecules/atoms, where N_A = 6.02214076 × 10²³.

The term “ideal gas” has been introduced by Rudolf Clausius in 1864. [35]

There is some debate as to whether Van der Waals forces can be said to include forces which act intramolecularly (between two different parts of the same molecule) as well as intermolecularly; however, it is probably logical to argue that a Van der Waals force should be one which can be described by the Van der Waals equation (Eq. 14.22), and specifically the constant a, which is only valid for intermolecular interactions. In this sense, all Van der Waals solids and even graphite can be considered molecular solids.

In Dutch names, the first “tussenvoegsel” (in this case “van”) should be lowercase only if it is preceded by the first name, so we would refer to Johannes Diderik van der Waals but Van der Waals forces. German literature of the time referred to “van der Waalsschen Kräfte” or “van der Waalsschen Kohäsionskräfte,” so “van der Waals forces” seems to have been the accepted form then, but that might have simply been in keeping with the usage of the German “von,” which is only ever capitalized when it occurs at the beginning of a sentence.

Note that this is the only definition for Van der Waals forces given in some texts.

Helium has the lowest melting point of any element. It can only be solidified below 1 K and even then only by simultaneously applying a pressure of more than 25 atm. Given these extreme conditions, there is significant error in measurements and so no general agreement on T_m. The melting of He has not been shown to require heat, i.e., it is not endothermic; however, there is no evidence to suggest that it is exothermic either. Its ΔH_f seems to be about 0.

And only about half of all hydrogen bonds are broken upon vaporization

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Titel: Covalent, Metallic, and Secondary Bonding
verfasst von: Rick Ubic
Verlag: Springer International Publishing
Buch: Crystallography and Crystal Chemistry
Print ISBN: 978-3-031-49751-3

Electronic ISBN: 978-3-031-49752-0

Copyright-Jahr: 2024
DOI: https://doi.org/10.1007/978-3-031-49752-0_14

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